A thermal insulation polymer material, its preparation method and application

Abstract

This invention provides a thermal insulation polymer material, its preparation method, and its application. The raw materials for preparing the thermal insulation polymer material include alcohol monomers, acid monomers, branched monomers, polymer polyols, etherified polyethylene glycol, isocyanate, and a catalyst. By adding branched monomers to participate in the polymerization reaction, hydroxyl groups are successfully introduced into the middle of the polyester chain segments. This allows the etherified polyethylene glycol structure to be introduced into the side chains of the polyester in subsequent reactions, resulting in a polyester material with a high phase change enthalpy, thus improving its heat storage and heat release capabilities.

Description

Technical Field

[0001] This invention belongs to the field of thermal insulation materials technology, specifically relating to a thermal insulation polymer material, its preparation method, and its application. Background Technology

[0002] Polyesters are a class of high molecular compounds obtained by catalytic esterification and vacuum polycondensation of polyols and polyacids. Polyesters are characterized by ester bonds as the main chain and have excellent comprehensive properties. As a raw material, they are widely used in the chemical fiber industry, and are also used in engineering plastics, bottles and films. They are widely used in the automotive, electrical appliance, decoration and packaging industries.

[0003] In the field of energy utilization, environmental protection is increasingly becoming an indispensable requirement, and thermal insulation materials have become a research hotspot. Among them, the design of thermal insulation materials based on the phase change process of matter has attracted the attention of many researchers. As we all know, materials absorb and release heat during phase change, and this process is reversible. Therefore, phase change can be used to store and release heat to achieve the purpose of thermal insulation, thus making phase change thermal storage materials have broad application prospects in heating, energy conservation, and waste heat recovery.

[0004] CN102604500A discloses a phase change thermal insulation interior wall coating, characterized by its composition: elastic emulsion, water, dispersant, wetting agent, thickener, preservative, hollow polyurethane microspheres, nano-titanium dioxide, opaque polymer, and water. The hollow polyurethane microspheres are encapsulated with polyethylene glycol, with a molecular weight between 1000 and 2000. This invention fully utilizes the physical changes of polyethylene glycol undergoing phase change at different temperatures, resulting in exothermic and endothermic reactions, thereby achieving temperature regulation. Simultaneously, the nano-titanium dioxide's light reflection provides radiative thermal insulation. The presence of the hollow expanded microspheres and the opaque polymer reduces the conductivity coefficient. By combining phase change, radiation, and conduction thermal insulation mechanisms, this coating is particularly suitable for use as a thermal insulation coating for interior surfaces. However, because the polyethylene glycol is physically encapsulated within the microspheres, during repeated phase change processes, the liquid polyethylene glycol easily flows out of the microspheres, causing the coating to lose its original temperature regulation function.

[0005] CN109762133A discloses a novel polymer-based phase change thermal storage material and its preparation method. This thermal storage material uses polyethylene glycol monomethyl ether (PEG) and polyethylene terephthalate (PET) as raw materials, 4,4-diphenylmethane diisocyanate (4,4-diphenylmethane diisocyanate) as a crosslinking agent, and dibutyltin maleate (Dibutyltin maleate) as a catalyst. The 4,4-diphenylmethane diisocyanate is used as a crosslinking agent to connect the terminal hydroxyl groups of PET with those of PEG, introducing chemical bonds between the PEG-1,4-diphenylmethane phase change material and the PET framework material, thus giving it solid-solid phase change properties. Although this method overcomes the leakage problem of polymer phase change materials prepared by physical methods, the number of PEG-1,4-diphenylmethane diisocyanates introduced through the terminal hydroxyl groups of PET is relatively small, resulting in a limited thermal storage capacity of the final material.

[0006] Therefore, in order to solve the above problems, it is urgent to develop a thermal insulation polymer material with excellent heat storage and release properties. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a thermal insulation polymer material, its preparation method, and its application. This thermal insulation polymer material, through the addition of branched monomers to participate in the polymerization reaction, successfully introduces hydroxyl groups into the middle of the polyester chain segments. This allows for the introduction of etherified polyethylene glycol structures into the side chains of the polyester in subsequent reactions, resulting in a polymer material with a high phase change enthalpy, thus exhibiting excellent heat storage and release properties, as well as superior mechanical and flame-retardant properties.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a heat-insulating polymer material, wherein the raw materials for preparing the heat-insulating polymer material include alcohol monomers, acid monomers, branched monomers, polymer polyols, etherified polyethylene glycol, isocyanates and catalysts.

[0010] The raw materials for preparing the thermal insulation polymer material provided by this invention include alcohol monomers, acid monomers, branched monomers, polymeric polyols, etherified polyethylene glycol, isocyanates, and catalysts. The four monomers—alcohol monomers, acid monomers, branched monomers, and polymeric polyols—are combined. The addition of branched monomers introduces hydroxyl groups into the middle of the polyester chain. These hydroxyl groups can react with isocyanates and etherified polyethylene glycol, introducing etherified polyethylene glycol into the side chains of the polyester. This results in the final copolymerized polyester having polyethylene glycol structures in its molecular chains, as well as etherified polyethylene glycol in its chain ends and side chains. Consequently, the final material contains polyethylene glycol soft segments in its chains, chain ends, and side chains, ensuring excellent mechanical and flame-retardant properties while also exhibiting a high phase change enthalpy and high heat storage and release capacity.

[0011] Preferably, the molar ratio of the alcohol monomer to the acid monomer is (1.5 to 2):1, for example, 1.55:1, 1.6:1, 1.65:1, 1.7:1, 1.75:1, 1.8:1, 1.85:1, 1.9:1 or 1.95:1, etc.

[0012] Preferably, the alcohol monomer comprises a small molecule diol.

[0013] Preferably, the small molecule diol includes any one or a combination of at least two of ethylene glycol, neopentyl glycol, 1,2-propanediol, 4,8-tricyclo[5.2.1.O2,7]decanediethanol, 1,4-cyclohexanediethanol, or 2-methyl-1,3-propanediol.

[0014] Preferably, the acid monomers include any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic anhydride, or dimethyl 2,6-naphthalenedicarboxylate.

[0015] Preferably, based on 100% of the molar amount of the acid monomer, the molar amount of the branched monomer is 1.0% to 5.0%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% or 5.5%, etc.

[0016] Preferably, the branched monomer comprises a polyol and / or a polyacid with a functionality of not less than 3 (e.g., 4, 5, 6, 7, 8 or 9), and more preferably any one or a combination of at least two of trimethylolpropane, pentaerythritol, glycerol or trimellitic anhydride.

[0017] Preferably, the molar percentage of the polymeric polyol is 3.0% to 6.0%, for example, 3.5%, 4%, 4.5%, 5%, or 5.5%, based on 100% of the molar percentage of the acidic monomer.

[0018] Preferably, the polymeric polyol includes any one or a combination of at least two of polyethylene glycol, polypropylene glycol, or polytetrahydrofuran.

[0019] Preferably, with the molar amount of the branched monomer being 100%, the molar amount of the etherified polyethylene glycol is 90-110%, such as 92%, 94%, 96%, 98%, 100%, 102%, 104%, 106%, or 108%.

[0020] Preferably, the etherified polyethylene glycol includes polyethylene glycol monomethyl ether (mPEG) and / or polyethylene glycol monobutyl ether.

[0021] Preferably, with the molar amount of the branched monomer being 100%, the molar amount of the isocyanate is 120% to 160%, for example, 125%, 130%, 135%, 140%, 145%, 150%, or 155%.

[0022] Preferably, the isocyanate comprises any one or a combination of at least two of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), or L-lysine diisocyanate (LDI).

[0023] Preferably, the present invention does not have a special limitation on the amount of catalyst used, and it can be added in accordance with the conventional addition amount in the art.

[0024] Preferably, the catalyst comprises any one or a combination of at least two of tetrabutyl titanate, tetraethyl titanate, dibutyltin oxide, tin chloride, stannous octoate, or dibutyltin maleate.

[0025] Preferably, the raw materials for preparing the heat-insulating polymer material also include any one or a combination of at least two of solvents, flame retardants, or other additives.

[0026] Preferably, the solvent includes acetone and / or dimethyl sulfoxide (DMSO).

[0027] Preferably, the flame retardant includes DOPO-MA and / or DOPO-ITA.

[0028] Preferably, the amount of flame retardant added is 1.0% to 5.0% based on 100% of the molar amount of the acid monomer, for example, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0% or 4.5%.

[0029] Preferably, the other additives include stabilizers.

[0030] Preferably, the stabilizer comprises trimethyl phosphate and / or triethyl phosphate.

[0031] Preferably, the number average molecular weight of the thermal insulation polymer material is 10,000 to 20,000, such as 11,000, 12,000, 13,000, 14,000, 15,000, 16,000, 17,000, 18,000 or 19,000.

[0032] Secondly, the present invention provides a method for preparing the thermal insulation polymer material as described in the first aspect, the preparation method comprising the following steps:

[0033] (1) An alcohol monomer, an acid monomer, a branched monomer, a catalyst and optionally a flame retardant are reacted to obtain an esterified product;

[0034] (2) The esterified product obtained in step (1), the polymer polyol and optional other auxiliaries are reacted to obtain the modified polyester;

[0035] (3) The modified polyester, etherified polyethylene glycol and isocyanate obtained in step (2) are reacted to obtain the heat insulation polymer material.

[0036] Preferably, the reaction in step (1) is carried out under normal pressure.

[0037] Preferably, the reaction in step (1) is carried out under stirring conditions, and more preferably under stirring conditions with a rotation speed of 60 to 100 r / min (e.g., 65 r / min, 70 r / min, 75 r / min, 80 r / min, 85 r / min, 90 r / min or 95 r / min, etc.).

[0038] Preferably, the reaction temperature in step (1) is 220 to 240°C, such as 222°C, 224°C, 226°C, 228°C, 230°C, 232°C, 234°C, 236°C, or 238°C.

[0039] Preferably, the reaction in step (2) specifically includes: first, an esterification reaction is carried out under normal pressure, and then a polycondensation reaction is carried out under a vacuum degree not higher than 100 Pa (e.g., 90 Pa, 80 Pa, 70 Pa, 60 Pa or 50 Pa).

[0040] Preferably, the esterification reaction time is 25 to 35 minutes, such as 26 minutes, 27 minutes, 28 minutes, 29 minutes, 30 minutes, 31 minutes, 32 minutes, 33 minutes, or 34 minutes.

[0041] Preferably, the temperature of the polycondensation reaction is 220–300°C, such as 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, or 290°C.

[0042] Preferably, the hydroxyl value of the system after the polycondensation reaction is 10-20 mg KOH / g, such as 11 mg KOH / g, 12 mg KOH / g, 13 mg KOH / g, 14 mg KOH / g, 15 mg KOH / g, 16 mg KOH / g, 17 mg KOH / g, 18 mg KOH / g, or 19 mg KOH / g.

[0043] Preferably, the reaction temperature in step (3) is 170 to 190°C, such as 172°C, 174°C, 176°C, 178°C, 180°C, 182°C, 184°C, 186°C or 188°C.

[0044] Preferably, the reaction time in step (3) is 3 to 5 hours, for example, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours or 4.8 hours.

[0045] Preferably, after the reaction in step (3) is completed, the steps of washing, filtering and drying are also included.

[0046] As a preferred embodiment of the present invention, the preparation method of the heat-insulating polymer material specifically includes the following steps:

[0047] (1) An esterification reaction is carried out on an alcohol monomer, an acid monomer, a branched monomer, a catalyst and optionally a flame retardant at atmospheric pressure, a temperature of 220-240°C and a rotation speed of 60-100°C to obtain an esterified product.

[0048] (2) The esterified product obtained in step (1), the polymer polyol and other optional additives are first subjected to an esterification reaction at atmospheric pressure and a temperature of 220-240°C for 25-35 minutes, and then subjected to a polycondensation reaction under a vacuum of no more than 100 Pa and a temperature of 220-300°C to obtain a modified polyester with a hydroxyl value of 10-20 mg KOH / g.

[0049] (3) The modified polyester, etherified polyethylene glycol and isocyanate obtained in step (2) are reacted at 170-190°C for 3-5 hours, washed, filtered and dried to obtain the heat-insulating polymer material.

[0050] Thirdly, the present invention provides the application of the thermal insulation polymer material as described in the first aspect in the preparation of thermal insulation fibers or thermal insulation adhesives.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] (1) The raw materials for preparing the heat-insulating polymer material provided by the present invention include alcohol monomers, acid monomers, branched monomers, polymer polyols, etherified polyethylene glycol, isocyanate and catalysts; by adding branched monomers to participate in the polymerization reaction, hydroxyl groups are successfully introduced into the middle of the polyester chain segment, so that the etherified polyethylene glycol structure can be introduced into the side chain of the polyester in the subsequent reaction, so that the obtained polymer material has a high phase change enthalpy and improves its heat storage and heat release capabilities.

[0053] (2) In addition, the heat-insulating polymer material provided by the present invention also has excellent flame retardant properties and mechanical properties.

[0054] (3) By further limiting the amount of branched monomers and polymer polyols, the present invention can make the final heat-insulating polymer material have a melting point of 122.9~137.2℃, a viscosity of 0.73~0.92dL / g, a phase change temperature of 34.4~37.2℃, a phase change enthalpy of 153~161J / g, and a flame retardant rating of V-0. Detailed Implementation

[0055] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0056] Example 1

[0057] A thermal insulation polymer material is prepared by the following steps:

[0058] (1) Add 150g terephthalic acid, 400g isophthalic acid, 200g dimethyl 2,6-naphthalenedicarboxylate, 200g ethylene glycol, 160g 4,8-tricyclo[5.2.1.O2,7]decanediethanol, 200g 2-methyl-1,3-propanediol, 25.12g trimethylolpropane, 0.15g tetrabutyl titanate and 28g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then increase the temperature by 0.5℃ / min, control the maximum temperature of the system to 235℃, and maintain this temperature for esterification until the by-product yield reaches more than 90% of the theoretical value. Stop esterification to obtain the esterified product.

[0059] (2) The temperature inside the stainless steel reactor was lowered to below 200℃, and 186.33g of polyethylene glycol (number average molecular weight of 1000) and 0.15g of trimethyl phosphate were added. The esterification reaction was carried out under normal pressure and stirring for 30min. The stirring rate was 60r / min. Then, the polycondensation reaction was carried out under a vacuum of below 100Pa. The maximum polycondensation reaction temperature was 260℃ and the reaction time was 4h. A modified polyester with a hydroxyl value of 14mgKOH / g was obtained.

[0060] (3) 186.33g of polyethylene glycol monomethyl ether (mPEG, number average molecular weight of 1000) and the modified polyester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, mPEG and acetone were mixed in a mass ratio of 1:3 to form an acetone solution of mPEG. Similarly, the modified polyester and dimethyl sulfoxide (DMSO) were mixed in a mass ratio of 1:3 to form a DMSO solution of modified polyester.

[0061] 55.89 g of MDI and 6.58 g of dibutyltin maleate were added to an acetone solution of mPEG and reacted at 70 °C for 30 min. Then, a DMSO solution of the modified polyester was added and reacted at 180 °C for 4 h at a rotation speed of 100 r / min. When the mixture became gel-like, it was taken out, washed, filtered, and soaked in water for 3 h. After filtration, the resulting gel was vacuum dried at 100 °C for 24 h to obtain the heat-insulating polymer material.

[0062] Example 2

[0063] A thermal insulation polymer material is prepared by the following steps:

[0064] (1) Add 200g phthalic anhydride, 200g isophthalic acid, 300g dimethyl 2,6-naphthalenedicarboxylate, 250g neopentyl glycol, 160g 4,8-tricyclo[5.2.1.O2,7]decanediethanol, 300g 1,4-cyclohexanediethanol, 20g pentaerythritol, 0.15g tetrabutyl titanate and 50g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then, increase the temperature at a rate of 0.5℃ / min until the maximum temperature reaches 230℃. Maintain this temperature for esterification until the byproduct yields more than 90% of the theoretical value. Stop esterification to obtain the esterified product.

[0065] (2) The temperature of the stainless steel reactor was lowered to below 200℃, and 330.52g of polyethylene glycol (number average molecular weight of 1500) and 0.15g of trimethyl phosphate were added. The esterification reaction was carried out under normal pressure for 30min. The reaction was carried out at a speed of 120r / min. Then, the polycondensation reaction was carried out under a vacuum of less than 100Pa. The maximum temperature of the polycondensation reaction was 250℃ and the time of the polycondensation reaction was 4h. A modified polyester with a hydroxyl value of 18mg KOH / g was obtained.

[0066] (3) 220.35g of mPEG (number average molecular weight of 1500) and the modified polyester ester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, mPEG and acetone were mixed in a mass ratio of 1:3 to form an acetone solution of mPEG. Similarly, modified polyester and DMSO were mixed in a mass ratio of 1:3 to form a DMSO solution of modified polyester.

[0067] 44.07 g MDI and 7.74 g dibutyltin maleate were added to an acetone solution of mPEG and reacted at 70 °C for 30 min. Then, a DMSO solution of the modified polyester was added and reacted at 100 r / min and 180 °C for 4 h. When the mixture became gel-like, it was taken out, washed, filtered, and soaked in water for 3 h. After filtration again, the gel was vacuum dried at 100 °C for 24 h to obtain the heat-insulating polymer material.

[0068] Example 3

[0069] A thermal insulation polymer material is prepared by the following steps:

[0070] (1) Add 300g phthalic anhydride, 150g terephthalic acid, 250g dimethyl 2,6-naphthalenedicarboxylate, 180g ethylene glycol, 200g neopentyl glycol, 200g 2-methyl-1,3-propanediol, 27g trimethylolpropane, 0.15g tetrabutyl titanate and 38g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then, increase the temperature to 235℃ at a rate of 0.5℃ / min and maintain this temperature for esterification until the byproduct yields more than 90% of the theoretical value. Stop esterification to obtain the esterified product.

[0071] (2) The temperature of the stainless steel reactor was lowered to below 200℃, and 447.19g of polyethylene glycol (number average molecular weight of 2000) and 0.15g of trimethyl phosphate were added. The reaction was carried out under normal pressure for 30min. The reaction was carried out under stirring conditions at a speed of 60r / min. Then, the polycondensation reaction was carried out under vacuum conditions below 100Pa. The maximum temperature of the polycondensation reaction was 260℃ and the reaction time was 4h. A modified polyester with a hydroxyl value of 15mg KOH / g was obtained.

[0072] (3) 401.45g of mPEG (number average molecular weight of 2000) and the modified polyester ester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, mPEG and acetone were mixed in a mass ratio of 1:3 to prepare an acetone solution of mPEG. Similarly, modified polyester and DMSO were mixed in a mass ratio of 1:3 to prepare a DMSO solution of modified polyester.

[0073] 60.05 g MDI and 8.61 g dibutyltin maleate were added to an acetone solution of mPEG and reacted at 70 °C for 30 min. Then, a DMSO solution of the modified polyester was added and reacted at 180 °C for 4 h at a rotation speed of 100 r / min. When the mixture became gel-like, it was taken out, washed, filtered, and soaked in water for 3 h. After filtration again, the gel was vacuum dried at 100 °C for 24 h to obtain the heat-insulating polymer material.

[0074] Example 4

[0075] A thermal insulation polymer material is prepared by the following steps:

[0076] (1) Add 150g terephthalic acid, 400g isophthalic acid, 200g dimethyl 2,6-naphthalenedicarboxylate, 8.26g trimellitic anhydride, 200g ethylene glycol, 200g 1,4-cyclohexanediol, 200g 2-methyl-1,3-propanediol, 0.15g tetrabutyl titanate and 35g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then, increase the temperature to 230℃ at a rate of 0.5℃ / min and maintain this temperature for esterification until the by-product yield reaches more than 90%. Stop esterification to obtain the esterified product.

[0077] (2) Cool the stainless steel reactor to below 200℃, add 357.769g of polyethylene glycol (number average molecular weight of 1500) and 0.15g of trimethyl phosphate and carry out esterification reaction for 30min under normal pressure. The esterification reaction is carried out under stirring at 80r / min. Then carry out polycondensation reaction under vacuum of less than 100Pa. The maximum temperature of polycondensation reaction is 270℃ and the time of polycondensation reaction is 4h to obtain modified polyester with hydroxyl value of 12mg KOH / g.

[0078] (3) 43.66g of mPEG (number average molecular weight of 1000) and the modified polyester ester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, mPEG and acetone were mixed in a mass ratio of 1:3 to form an acetone solution of mPEG. Similarly, modified polyester and DMSO were mixed in a mass ratio of 1:3 to form a DMSO solution of modified polyester.

[0079] 12.91 g MDI and 6.93 g dibutyltin maleate were added to an acetone solution of mPEG and reacted at 70 °C for 30 min. Then, a DMSO solution of the modified polyester was added and reacted at 180 °C for 4 h at a rotation speed of 100 r / min. When the mixture became gel-like, it was taken out, washed, filtered, and soaked in water for 3 h. After filtration again, the gel was vacuum dried at 100 °C for 24 h to obtain the heat-insulating polymer material.

[0080] Example 5

[0081] A thermal insulation polymer material is prepared by the following steps:

[0082] (1) Add 150g terephthalic acid, 400g isophthalic acid, 200g dimethyl 2,6-naphthalenedicarboxylate, 12.49g trimellitic anhydride, 300g neopentyl glycol, 100g 1,2-propanediol, 160g 4,8-tricyclo[5.2.1.O2,7]decanediethanol, 200g 2-methyl-1,3-propanediol, 32g trimethylolpropane, 0.15g tetrabutyl titanate and 35g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then, increase the temperature to 220℃ at a rate of 0.5℃ / min and maintain this temperature until the by-product yield reaches more than 90%. Stop the esterification to obtain the esterified product.

[0083] (2) The temperature inside the stainless steel reactor was lowered to below 200℃, and 195.18g of polyethylene glycol (number average molecular weight of 1500) and 0.15g of trimethyl phosphate were added. The esterification reaction was carried out under normal pressure for 30min. The esterification reaction was carried out under a stirring rate of 100r / min. Then, the polycondensation reaction was carried out under a vacuum of less than 100Pa. The maximum polycondensation temperature was 280℃ and the polycondensation reaction time was 4h. A modified polyester with a hydroxyl value of 12mg KOH / g was obtained.

[0084] (3) 97.55g of mPEG (number average molecular weight of 1500) and the modified polyester ester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, mPEG and acetone were mixed in a mass ratio of 1:3 to form an acetone solution of mPEG. Similarly, modified polyester and DMSO were mixed in a mass ratio of 1:3 to form a DMSO solution of modified polyester.

[0085] 19.5 g of MDI and 7.01 g of dibutyltin maleate were added to an acetone solution of mPEG and reacted at 70 °C for 30 min. Then, a DMSO solution of the modified polyester was added and reacted at 180 °C for 4 h at a rotation speed of 100 r / min. When the mixture became gel-like, it was taken out, washed, filtered, and soaked in water for 3 h. After filtration again, the gel was vacuum dried at 100 °C for 24 h to obtain the heat-insulating polymer material.

[0086] Example 6

[0087] A thermal insulation polymer material is prepared by the following steps:

[0088] (1) Add 150g terephthalic acid, 400g isophthalic acid, 200g dimethyl 2,6-naphthalenedicarboxylate, 300g neopentyl glycol, 300g 4,8-tricyclo[5.2.1.O2,7]decanediethanol, 200g 2-methyl-1,3-propanediol, 11.81g trimethylolpropane, 0.15g tetrabutyl titanate and 35g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then, increase the temperature at a rate of 0.5℃ / min until the maximum temperature reaches 240℃. Maintain this temperature until the by-product yield reaches more than 90%, then stop esterification to obtain the esterified product.

[0089] (2) The temperature inside the stainless steel reactor was lowered to below 200℃, and 195.18g of polyethylene glycol (number average molecular weight of 1500) and 0.15g of trimethyl phosphate were added. The esterification reaction was carried out under normal pressure for 30min. The esterification reaction was carried out under a stirring rate of 100r / min. Then, the polycondensation reaction was carried out under a vacuum of less than 100Pa. The maximum temperature of the polycondensation reaction was 250℃, and the polycondensation reaction time was 4h. A modified polyester with a hydroxyl value of 13mg KOH / g was obtained.

[0090] (3) 176.33g of mPEG (number average molecular weight of 2000) and the modified polyester ester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, mPEG and acetone were mixed in a mass ratio of 1:3 to prepare an acetone solution of mPEG. Similarly, modified polyester and DMSO were mixed in a mass ratio of 1:3 to prepare a DMSO solution of modified polyester.

[0091] Based on 100% mPEG by mass, 26.4g MDI and 7.39g dibutyltin maleate were added to an acetone solution of mPEG and reacted at 70℃ for 30min. Then, a DMSO solution of the modified polyester was added, and the reaction was maintained at 180℃ for 4h at a rotation speed of 100r / min. When the mixture became gel-like, it was taken out, washed, filtered, and then soaked in water for 3h. After filtration again, the resulting gel was vacuum dried at 100℃ for 24h to obtain the heat-insulating polymer material.

[0092] Example 7

[0093] A thermal insulation polymer material is prepared by the following steps:

[0094] (1) Add 150g terephthalic acid, 400g isophthalic acid, 200g dimethyl 2,6-naphthalenedicarboxylate, 200g ethylene glycol, 160g 4,8-tricyclo[5.2.1.O2,7]decanediethanol, 200g 2-methyl-1,3-propanediol, 25.12g trimethylolpropane, 0.15g tetrabutyl titanate and 28g DOPO-MA to a 2L stainless steel reactor. After heating to 140℃, start stirring and set the stirring rate to 60r / min. Then increase the temperature by 0.5℃ / min, control the maximum temperature of the system to 235℃, and maintain this temperature for esterification until the by-product yield reaches more than 90% of the theoretical value. Stop esterification to obtain the esterified product.

[0095] (2) The temperature inside the stainless steel reactor was lowered to below 200℃, and 186.33g of polyethylene glycol (number average molecular weight of 1000) and 0.15g of trimethyl phosphate were added. The esterification reaction was carried out under normal pressure and stirring for 30min. The stirring rate was 60r / min. Then, the polycondensation reaction was carried out under a vacuum of below 100Pa. The maximum polycondensation reaction temperature was 260℃ and the reaction time was 4h. A modified polyester with a hydroxyl value of 14mgKOH / g was obtained.

[0096] (3) 186.33g of polyethylene glycol monobutyl ether (number average molecular weight of 1000) and the modified polyester obtained in step (2) were vacuum dried at 100℃ for 1h. Then, polyethylene glycol monobutyl ether and acetone were mixed in a mass ratio of 1:3 to form a polyethylene glycol monobutyl ether acetone solution. Similarly, the modified polyester and dimethyl sulfoxide (DMSO) were mixed in a mass ratio of 1:3 to form a modified polyester DMSO solution.

[0097] Based on 100% mPEG mass, 55.89g MDI and 6.58g dibutyltin maleate were added to an acetone solution of polyethylene glycol monobutyl ether and reacted at 70℃ for 30min. Then, a DMSO solution of the modified polyester was added, and the reaction was maintained at 180℃ for 4h at a rotation speed of 100r / min. When the mixture became gel-like, it was taken out, washed, filtered, and soaked in water for 3h. After filtration, the resulting gel was vacuum dried at 100℃ for 24h to obtain the heat-insulating polymer material.

[0098] Example 8

[0099] A heat-insulating polymer material, which differs from Example 1 only in that the amount of polyethylene glycol added in step (2) is 62.11g, while the other components, conditions and parameters are the same as in Example 1.

[0100] Example 9

[0101] A heat-insulating polymer material, which differs from Example 1 only in that the amount of polyethylene glycol added in step (2) is 372.73g, while the other components, conditions and parameters are the same as in Example 1.

[0102] Example 10

[0103] A heat-insulating polymer material, which differs from Example 1 only in that the amount of trimethylolpropane added in step (1) is 34.27g, the polycondensation temperature is 240℃, the polycondensation time is 3h, and the other components, conditions and parameters are the same as in Example 1.

[0104] Comparative Example 1

[0105] A heat-insulating polymer material, which differs from Example 1 only in that polyethylene glycol is not added in step (2) and polyethylene glycol monomethyl ether is not added in step (3). Other components, conditions and parameters are the same as in Example 1.

[0106] Comparative Example 2

[0107] A heat-insulating polymer material, which differs from Example 1 only in that trimethylolpropane is not added in step (1), while the other components, conditions and parameters are the same as in Example 1.

[0108] Performance testing:

[0109] (1) Flame retardancy: The test standard refers to the UL 94 vertical burning test method, and the flame retardancy rating standard is as follows:

[0110] V0: After two 10-second burning tests on the sample, the flame extinguishes within 30 seconds and no burning material falls off; V1: After two 10-second burning tests on the sample, the flame extinguishes within 60 seconds and no burning material falls off; V2: After two 10-second burning tests on the sample, the flame extinguishes within 60 seconds and burning material falls off.

[0111] (2) Viscosity: Tested according to GB / T 14190 2008 Fiber Grade Polyester Chips (PET);

[0112] (3) Melting point, phase transition temperature and phase transition enthalpy: The TAQ20 differential scanning calorimeter was used for testing. The flow rate under nitrogen atmosphere was 20 mL / min. During the test, 5 mg of sample was placed in an alumina sample pan. The test process was as follows: The sample was heated from 30 °C to 180 °C at a heating rate of 10 °C / min. It was held in this state for 2 min to eliminate thermal history. The sample was then cooled to 30 °C at a cooling rate of 10 °C / min. Subsequently, the sample underwent a second heating process, from 30 °C to 180 °C at a heating rate of 10 °C / min. The melting point, phase transition temperature and phase transition enthalpy of the sample were obtained from the second heating process.

[0113] The thermal insulation polymer materials provided in Examples 1-10 and Comparative Examples 1-2 were tested according to the above test methods. The test results are shown in Table 1.

[0114] Table 1

[0115]

[0116]

[0117] According to the data in Table 1:

[0118] The thermal insulation polymer materials obtained in Examples 1-7 have melting points of 122.9-137.2℃, viscosity of 0.73-0.92 dL / g, phase change temperature of 34.4-37.2℃, phase change enthalpy of 153-161 J / g, and flame retardancy ratings of V-0.

[0119] Comparing the data of Example 1 and Comparative Example 1, it can be seen that the polymer material obtained by not adding polyethylene glycol in step (2) and not adding polyethylene glycol monomethyl ether in step (3) has too high a melting point and cannot undergo phase change.

[0120] Comparing the data of Example 1 and Comparative Example 2, it can be seen that the phase change enthalpy of the polymer material obtained in step (1) without the addition of trimethylolpropane is lower, indicating that the heat storage and release capacity is poor.

[0121] Further comparison of the data from Examples 1 and 8-9 shows that a lower amount of polyethylene glycol in step (2) (Example 8) will result in a lower phase change enthalpy of the prepared thermal insulation polymer material; while a higher amount of polyethylene glycol in step (2) (Example 9) will result in a lower melting point of the final thermal insulation polymer material.

[0122] Finally, comparing the data from Example 1 and Example 10, it can be seen that if the amount of trimethylolpropane used in step (1) is high, the material is prone to cross-linking, requiring a reduction in polycondensation temperature or time, resulting in a lower viscosity of the final polyester material.

[0123] The applicant declares that this invention illustrates a thermal insulation polymer material, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. A thermal insulation polymer material, characterized by, The preparation raw material of the heat insulation high polymer material comprises alcohol monomer, acid monomer, branched monomer, polymer polyol, etherified polyethylene glycol, isocyanate and catalyst; The branched monomer comprises any one or combination of at least two of trimethylolpropane, pentaerythritol, glycerol or trimellitic anhydride; The molar number of the branched monomer is 1.0-5.0% based on 100% of the molar number of the acid monomer, and the molar number of the polymer polyol is 3.0-6.0%; The molar ratio of the alcohol monomer and the acid monomer is (1.5-2):1; The polymer polyol comprises polyethylene glycol; The heat insulation high polymer material is prepared by the following method, and the preparation method comprises the following steps: (1) reacting alcohol monomer, acid monomer, branched monomer, catalyst and optionally flame retardant to obtain esterification product; (2) reacting the esterification product obtained in step (1), polymer polyol and optionally other auxiliary agents to obtain modified polyester; (3) reacting the modified polyester obtained in step (2), etherified polyethylene glycol and isocyanate to obtain the heat insulation high polymer material.

2. The thermally insulated polymer material according to claim 1, characterized in that, The alcohol monomer comprises small molecule dihydric alcohol.

3. The thermally insulated polymer material according to claim 2, characterized in that The small molecule dihydric alcohol comprises any one or combination of at least two of ethylene glycol, neopentyl glycol, 1,2-propanediol, 4,8-tricyclo[5.2.1.02,7]decane dimethyl alcohol, 1,4-cyclohexane dimethyl alcohol or 2-methyl-1,3-propanediol.

4. The thermally insulated polymer material according to claim 1, wherein The acid monomer comprises any one or combination of at least two of terephthalic acid, isophthalic acid, phthalic anhydride or 2,6-naphthalene dimethyl acid dimethyl ester.

5. The thermally insulated polymer material according to claim 1, wherein The polymer polyol further comprises any one or combination of at least two of polypropylene glycol or polytetrahydrofuran.

6. The thermally insulated polymer material according to claim 1, wherein The molar number of the etherified polyethylene glycol is 90-110% based on 100% of the molar number of the branched monomer.

7. The thermally insulated polymer material according to claim 1, wherein The etherified polyethylene glycol comprises polyethylene glycol monomethyl ether and / or polyethylene glycol monobutyl ether.

8. The thermally insulated polymer material according to claim 1, wherein The molar number of the isocyanate is 120-160% based on 100% of the molar number of the branched monomer.

9. The thermally insulated polymer material according to claim 1, wherein The isocyanate comprises any one or combination of at least two of toluene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hexamethylene diisocyanate or L-lysine diisocyanate.

10. The thermally insulated polymer material according to claim 1, wherein The catalyst comprises any one or combination of at least two of tetrabutyl titanate, tetraethyl titanate, dibutyl tin oxide, tin chloride, stannous octoate or dibutyl tin maleate.

11. The thermally insulated polymer material according to claim 1, wherein The preparation raw material of the heat insulation high polymer material further comprises any one or combination of at least two of solvent, flame retardant or other auxiliary agent.

12. The thermally insulating polymer material of claim 11, wherein, The solvent comprises acetone and / or dimethyl sulfoxide.

13. The thermally insulating polymer material of claim 11, wherein, The flame retardant comprises DOPO-MA and / or DOPO-ITA.

14. The thermally insulating polymer material of claim 11, wherein, The molar number of the flame retardant is 1.0-5.0% based on 100% of the molar number of the acid monomer.

15. The thermally insulating polymer material of claim 11, wherein, The other auxiliary agent comprises stabilizer.

16. The thermally insulating polymer material of claim 15, wherein, The stabilizer comprises trimethyl phosphate and / or triethyl phosphate.

17. The thermally insulating polymer material of claim 1, wherein, The number average molecular weight of the heat insulation high polymer material is 10000-20000.

18. A method of preparing the thermal insulation polymer material according to any one of claims 1 to 17, characterized in that, The preparation method comprises the following steps: (1) reacting an alcohol monomer, an acid monomer, a branched monomer, a catalyst and optionally a flame retardant to obtain an esterification product; (2) reacting the esterification product obtained in step (1), a polymer polyol and optionally other auxiliaries to obtain a modified polyester; (3) reacting the modified polyester obtained in step (2), an etherified polyethylene glycol and an isocyanate to obtain the thermal insulation high polymer material.

19. The method of claim 18, wherein, The reaction in step (1) is carried out under normal pressure.

20. The method of claim 18, wherein, The reaction in step (1) is carried out under stirring.

21. The method of claim 20, wherein, The stirring is carried out at a stirring speed of 60-100 r / min.

22. The method of claim 18, wherein, The reaction in step (1) is carried out at a temperature of 220-240 ℃.

23. The preparation method according to claim 18, characterized in that, The reaction in step (2) specifically comprises: first, carrying out an esterification reaction under normal pressure, and then carrying out a polycondensation reaction under a vacuum degree of not higher than 100 Pa.

24. The method of claim 23, wherein, The esterification reaction is carried out for 25-35 min.

25. The preparation method according to claim 23, characterized in that, The polycondensation reaction is carried out at a temperature of 220-300 ℃.

26. The preparation method according to claim 23, characterized in that, The hydroxyl value of the system after the polycondensation reaction is 10-20 mg KOH / g.

27. The method of claim 18, wherein the method further comprises, The reaction in step (3) is carried out at a temperature of 170-190 ℃.

28. The method of claim 18, wherein the method further comprises, The reaction in step (3) is carried out for 3-5 h.

29. The method of claim 18, wherein the method further comprises, After the reaction in step (3) is completed, the steps of washing, filtering and drying are further included.

30. Use of the thermal insulation high polymer material as claimed in any one of claims 1-17 in the preparation of thermal insulation fibers or thermal insulation glue.

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